KR20240054336A - Thermosetting compositions based on (meth)acrylates and peroxodicarbonates - Google Patents

Abstract

The present invention relates to a thermosetting composition comprising: (A) at least one radically curable compound, wherein the radically curable compound comprises at least one (meth)acrylate, (B) a peroxo compound. at least one radical initiator based on, wherein the peroxo compound comprises at least one peroxodicarbonate, (C) at least one stabilizer comprising at least one conformationally hindered phenol. and (D) at least one synergist based on carbon variants with unsaturated carbon-carbon bonds.

Description

Thermosetting compositions based on (meth)acrylates and peroxodicarbonates

The present invention relates to thermosetting compositions based on (meth)acrylates and peroxodicarbonates. The invention also relates to the use of the composition as a sealing, adhesive and/or encapsulant composition.

In the latest technology. Various peroxides are known to be used as initiators for the radical polymerization of compositions based on ethylenically unsaturated compounds.

Common peroxo compounds include peroxo(di)esters, hydroperoxides, (di)alkyl peroxides, ketone peroxides, perketals, peracids, peroxomonocarbonates, and peroxodicarbonates. An overview of peroxo compounds suitable as initiators and their thermal properties, especially the 1 hour half-life temperature, is given in Pergan's brochure “Polymerization of monomers with Organic Peroxides for the High Polymer Industry".

The one-hour half-life temperature is the temperature at which half of a given amount of peroxide decomposes in one hour. Typically, the half-life temperature of a peroxide is determined in a 0.1 molar solution of monochlorobenzene. Therefore, half-life is the time for half of a given amount of peroxide to decompose at a particular temperature.

The peroxo compounds mentioned are very diverse in terms of reactivity. For example, while most hydroperoxides can be easily stored at room temperature for several months, many peroxodicarbonates have a one-hour half-life temperature of about 60°C and cannot be stored permanently at room temperature.

EP 0 245 728 A2 discloses a process for producing scratch-resistant coatings by thermally polymerizing (meth)acrylate-containing formulations using peroxides with a half-life of less than 2 minutes at 100°C. there is. In particular, the use of dialkyl peroxodicarbonates is shown to be advantageous because they can be activated at low temperatures and coatings cured with them have high scratch resistance. The use of stabilizers is not disclosed in the specification. The described preparations have a short processing time at room temperature and can be stored for only a limited time even at low temperatures.

WO 2018/089494 A1 describes both thermosetting and dual-curing (meth)acrylate systems. It is characterized by a high glass transition temperature of over 85°C in the cured state and a low curing temperature of below 80°C. High reactivity is achieved by using aliphatic peroxodicarbonate. However, the described compositions have insufficient stability at room temperature, which can be disadvantageous and costly in industrial processes during downtime, especially when using large adhesive containers. After a correspondingly long holdup time at room temperature, the composition tends to partially harden and therefore cannot be dosed in a process-safe manner.

In particular, an approach for stabilizing reactive peroxodicarbonates is described in US 5 155 192 A. For this purpose, a small amount of hydroperoxide is added to the peroxodicarbonate. However, the use of reactive (meth)acrylate agents has not been described. Addition of hydroperoxide appears to reduce the reactivity of peroxodicarbonate.

US 5 548 046 describes the stabilization of dialkyl peroxodicarbonates by methacrylonitrile in the context of the production of PVC.

US 2004/0211938 A1 describes a method for stabilizing peroxodicarbonate by adding propiolic acid. No curable formulations based on (meth)acrylates are disclosed.

A comprehensive description of additional approaches for stabilizing peroxodicarbonate is disclosed in WO 2003/002527 A1.

US 10 982 120 B2 describes an electrically conductive composition containing, in addition to electrically conductive particles, at least one organometallic complex that has a positive effect on the contact resistance of the cured composition. As an initiator system for (meth)acrylate resins, peroxodicarbonates are described, which are additionally stabilized by hindered phenols. An unfilled system is not provided.

The various formulations described in the state of the art are aimed solely at stabilizing peroxodicarbonate. In all these descriptions, the storage stability of the peroxodicarbonate-containing composition as high as possible is of utmost importance. However, no composite composition is disclosed. This is because stabilized peroxides are sometimes used for large-scale polymerization of common monomers such as ethene, propene or vinyl chloride. In these processes, long processing times at room temperature or starting temperatures as low as possible are not critical.

The object of the present invention is to provide compositions based on (meth)acrylates and peroxodicarbonates that avoid the disadvantages of the compositions known from the state of the art and can be used even in complex industrial processes as sealing, adhesive and/or encapsulant compositions. It is provided.

According to the invention, this object is solved by the thermosetting composition according to claim 1.

Advantageous embodiments of the compositions according to the invention are specified in the subclaims, which can optionally be combined with one another.

According to the invention, the thermosetting composition has the following components:

(A) at least one radically polymerizable compound, wherein the radically polymerizable compound includes at least one (meth)acrylate,

(B) at least one radical initiator based on a peroxo compound, wherein the peroxo compound comprises at least one peroxodicarbonate,

(c) one or more stabilizers comprising at least one sterically hindered phenol, and

(D) at least one synergist based on a carbon allotrope with unsaturated carbon-carbon bonds.

The composition according to the invention is liquid at room temperature and preferably exists as a single-component composition. However, the composition may also be provided in multicomponent form.

The liquid composition is characterized by high reactivity and at the same time long processing times at room temperature. Due to the long processing time at room temperature, the composition can also be easily used in complex industrial processes even after long downtimes. In particular, the composition does not need to be removed from the plant and transferred to cold storage cells, even during long-term dosing interruptions.

By exposure to heat, the compositions according to the invention can be cured even at low temperatures. Optionally, the composition may be further fixed by exposure to actinic radiation.

Another object of the present invention is to use the composition as a sealing, adhesive and/or encapsulant composition.

Additionally, methods of using the composition to bond, encapsulate or coat a substrate are proposed. This method involves the following steps:

a) providing a composition according to the invention;

b) dosing the composition onto a first substrate;

c) optionally supplying a second substrate to the composition;

d) optionally fixing the composition by actinic irradiation; and

e) curing the composition while heating the composition at a temperature of 60 to 100° C. for 5 to 60 minutes.

In the attached drawing:
Figure 1 shows the DSC curves of a composition not according to the invention and a composition according to the invention.

Hereinafter, the present invention will be described in detail and illustratively by way of preferred embodiments, but should not be construed as limiting.

In the meaning of the present invention, "liquid" means that the loss modulus G", as determined by measuring the viscosity at 23° C., is greater than the storage modulus G' of the respective composition.

As long as the indefinite article (“a” or “an”) is used, the plural form “one or more” is also included unless explicitly excluded.

“At least bifunctional” means that 2 or more units of each functionality mentioned are contained per molecule.

In the meaning of the present invention, “single-component” or “single-component composition” means that the components of the composition mentioned are present together in a common packaging unit, i.e. not stored separately.

“Multicomponent” or “multicomponent composition” means that the reactive components of the composition are present separately in two or more packaging units.

Compositions are considered “processable” if the viscosity of each readily mixed composition increases by less than 30% while stored at room temperature for at least 72 hours.

Below, each component of the composition according to the invention will be described separately. However, the individual components may be combined with each other in any way.

Component (A): Radically polymerizable compound

The composition contains at least one radically polymerizable compound (A) comprising at least one (meth)acrylate. In the meaning of the present invention, the term “(meth)acrylate” includes both acrylates and similar methacrylates.

In terms of structure, the (meth)acrylates of component (A) are no longer limited and include, for example, linear, branched, aliphatic, aromatic and heterocyclic (meth)acrylates and combinations thereof.

Also, in the meaning of the present invention, (meth)acrylates are monomeric, oligomeric or polymer compounds as long as they contain at least one radically crosslinkable (meth)acrylate group.

In one embodiment, the radically curable compound (A) may comprise one or several polyfunctional (meth)acrylates.

Examples of monofunctional aliphatic (meth)acrylates are isobutyl (meth)acrylate, isooctyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isononyl (meth)acrylate. , Ethylhexyl (meth)acrylate, 2-propylheptyl (meth)acrylate, 4-methyl-2-propylhexyl (meth)acrylate, pentadecyl (meth)acrylate, cetyl (meth)acrylate, 2-hyde. Roxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, palmitolyl (meth)acrylate )acrylate, heptadecyl (meth)acrylate and stearyl (meth)acrylate.

Examples of monofunctional alicyclic (meth)acrylates include cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, cyclic trimethylolpropane formyl (meth)acrylate, and dicyclopentenyl (meth)acrylate. , dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, tert-butylcyclohexanol methacrylate and octahydro-4,7-methano-1H-indenylmethyl (meth)acrylate.

Examples of monofunctional aromatic (meth)acrylates are 2-(o-phenylphenoxy)ethyl (meth)acrylate, 2-(o-phenoxy)ethyl (meth)acrylate, ortho-phenylbenzyl (meth)acrylate. acrylate, ethoxylated nonylphenol (meth)acrylate and ethoxyphenyl acrylate.

Examples of heterocyclic, ethoxylated and additional monofunctional meta(acrylates) include tetrahydrofurfuryl (meth)acrylate, (2-ethyl-2-methyl-1,3-dioxolat-4-yl)methyl acrylate ester, 5-ethyl-1,3-dioxan-5-yl)methyl acrylate, caprolactone (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate and alkoxylated lauryl. It is acrylate.

In addition to monofunctional (meth)acrylates, component (A) may also comprise bifunctional (meth)acrylates or (meth)acrylates of higher functionality, preferably as crosslinking agent.

Examples of difunctional (meth)acrylates or of higher functionality are hexanediol di(meth)acrylate, di(trimethylpropane) tetraacrylate, 4-butanediol di(meth)acrylate, tripropylene. Glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate Rate, cyclohexane dimethylol di(meth)acrylate, nonanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tris-(2-hydroxyethyl)isocyanurate tri(meth)acrylate ester, pentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, BPA-diepoxypropane diacrylate and ethoxylated bisphenol-A di(meth)acrylate.

For example, the (meth)acrylates mentioned are commercially available from Arkema Sartomer, BASF, IMG Resins, Sigma Aldrich or TCI.

Urethane (meth)acrylates based on polyesters, polyacrylates, polyisoprene, polyethers, polycarbonate diols and/or (hydrogenated) polybutadiene diols can be used as high molecular weight radically polymerizable compounds.

In addition to monofunctional (meth)acrylates, component (A) preferably comprises at least bifunctional crosslinking agents based on aliphatic and/or aromatic urethane (meth)acrylates.

Examples of suitable commercially available urethane (meth)acrylates include Visiomer HEMA-TMDI available from Evonik, SUO-1020 NI (polycarbonate based) or SUO-H8628 (polybutadiene based) available from Shin-A T&C. , CN9014NS available from Sartomer, UV-3200B (polyester type) available from Nippon Goshei, or XMAP type (polyacrylate type) available from Kaneka.

Further radically polymerizable compounds (A) that can be used in the sense of the present invention include acrylic and methacrylic acids, acrylamide, acryloyl morpholine, bismaleimide, vinyl methyl oxazolidinone (VMOX), N-vinyl capro. Lactams, N-vinyl compounds such as N-vinyl pyrrolidone and N-vinyl imidazole, and 1,3,5-triazine-2,4,6(1H,3H,5H) commercially available as TAICROS ^® -It is a compound with an allyl group such as trion.

Polybutadiene with unhydrogenated free double bonds, such as Poly BD ^® type, can also be used as a radically polymerizable compound.

The above list of suitable material types is illustrative and should not be construed as limiting.

In the composition according to the invention, component (A) is preferably present in an amount of 5 to 98 wt%, preferably 10 to 90 wt%, based on the total weight of components (A) to (E) of the composition, as defined below. or present in a proportion of 20 to 85 wt%.

The weight ratio of monofunctional (meth)acrylate in component (A) is preferably 1 to 95%, more preferably 1 to 80% or 1 to 60%.

Component (B): Radical polymerization initiator

In addition to component (A), the composition according to the invention comprises at least one radical polymerization initiator (B) based on a peroxo compound (B1), wherein the peroxo compound comprises at least one peroxodicarbonate. .

Examples of suitable peroxodicarbonates are di-(4-tert-butylcyclohexyl) peroxodicarbonate, di-(2-ethylhexyl) peroxodicarbonate, di-n-butyl peroxodicarbonate, dicetyl peroxodicarbonate. Includes oxodicarbonate, dimyristyl peroxodicarbonate, and mixtures thereof.

Further suitable peroxo compounds (B1) are, for example, peroxo(di)esters, hydroperoxides, (di)alkyl peroxides, ketone peroxides, perketals, peracids and peroxomonocarbonates.

Examples of suitable peroxoesters include cumol peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, tert-amyl peroxyneodecanoate, tert-butyl peroxyneodecanoate. Decanoate, 1,1,3,3-tetramethylbutyl peroxypivalate, tert-amyl peroxypivalate, tert-butyl peroxypivalate, didecanoyl peroxide, dilauroyl peroxide, 2, 5-dimethyl-2,5-di(2-ethylhexanoylperoxy) hexane, 1,1,3,3-tetramethylbutyl-peroxy-2-ethylhexanoate, tert-amyl peroxy-2- Ethylhexanoate, dibenzoyl peroxide, tert-butyl-peroxy-2-ethylhexanoate, tert-butyl peroxyisobutyrate, tert-butyl-peroxy-3,5,5-trimethyl hexanoate, Includes tert-butyl peroxyacetate and tert-butyl peroxybenzoate.

Examples of suitable hydroperoxides are di-isopropylbenzene monohydroperoxide, p-menthane hydroperoxide, cumol hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butyl hydroperoxide. and tert-amyl hydroperoxide.

Examples of suitable alkyl peroxides (B1-c) are diisobutyryl peroxide, di-(3,5,5-trimethylhexanoyl) peroxide, 1,1-di-(tert-butylperoxy)-3 ,3,5-trimethyl cyclohexane, 1,1-di-(tert-butylperoxy)cyclohexane, 2,2-di-(tert-butylperoxy)butane, di-tert-amyl peroxide, dicumyl Peroxide, di-(2-tert-butyl-peroxyisopropyl)benzene, 2,5-dimethyl-2,5-di-(tert-butylperoxy) hexane, tert-butylcumyl peroxide, 2,5 -dimethyl-2,5-di(tert-butylperoxy)hexyne and di-tert-butyl peroxide.

Examples of suitable peroxomonocarbonates include tert-amyl-peroxy-2-ethylhexyl carbonate, tert-butyl-peroxyisopropyl carbonate and tert-butyl-peroxy-2-ethylhexyl carbonate.

In the composition according to the present invention, the peroxo compound (B1) is present in a proportion of 0.01 to 10 wt%, preferably 0.1 to 5 wt%, based on the total weight of the composition.

The proportion of peroxodicarbonate in the peroxo compound (B1) is at least 10 wt%, preferably 50 to 100 wt%. In an advantageous embodiment, the peroxo compound (B1) is a peroxodicarbonate or a mixture of several peroxodicarbonates.

In addition, the composition may also contain at least one radical photoinitiator (B2), which allows the composition according to the invention to be fixed by light.

The radical photoinitiator used in the composition according to the invention as component (B2) can be activated by exposure to actinic radiation, preferably with a wavelength of 200 to 600 nm, particularly preferably 320 to 480 nm. If necessary, the radical photoinitiator may be combined with an appropriate photosensitizer.

α-Hydroxy ketone, benzophenone, α,α'-diethoxy acetophenone, 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, 4-isopropylphenyl-2-hydroxy -2-Propyl-ketone, 4,4-bis(diethylamino)benzophenone, 2-thylhexyl-4-(dimethylamino)benzoate, ethyl-4-(dimethylamino)benzoate, 2-butoxyethyl -4-(dimethylamino)benzoate, 1-hydroxycyclohexylphenyl ketone, isoamyl-p-dimethyl aminobenzoate, methyl-4-dimethyl aminobenzoate, methyl-o-benzoyl benzoate, benzoin, benzoate Phosphorus ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-isopropyl thioxanthone, dibenzosuberone, ethyl-( 3-benzoyl-2,4,6-trimethylbenzoyl)(phenyl)phosphinate, methyl benzoyl formate, oxime ester, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl-(2,4, Common commercially available compounds such as 6-trimethylbenzoyl)phenylphosphinate and bisacylphosphine oxide can be used as radical photoinitiators (B2).

Radical photoinitiators that can be activated by exposure to actinic radiation are called UV photoinitiators.

For example, IRGACURE 184, IRGACURE 500, IRGACURE 1179, IRGACURE 2959, IRGACURE 745, IRGACURE 651, IRGACURE 369, IRGACURE 907, IRGACURE 1300, IRGACURE 819, IRGACURE 819DW, IRGACURE 2022, IRGACURE 2100, IRGACURE 784, IRGACURE 250, IRGACURE TPO, IRGACURE ^TM type from BASF SE such as IRGACURE TPO-L type can be used as UV photoinitiator. Additionally, DAROCUR ^TM types from BASF SE can be used, for example DAROCUR MBF, DAROCUR 1173, DAROCUR TPO and DAROCUR 4265 types.

The above list of suitable material types is illustrative and should not be construed as limiting.

In the composition according to the invention, the radical photoinitiator (B2) is optionally present in a proportion of 0.01 to 7 wt% based on the total weight of components (A) to (E) of the composition.

Ingredient (C): Stabilizer

In addition to components (A) and (B), the composition according to the invention comprises at least one stabilizer (C) comprising at least one conformationally hindered phenol (C1).

A particularly advantageous combination of the reactivity of the curable composition and a long processing time at room temperature can be achieved by using a conformationally hindered phenol (C1) with a molar mass of less than 500 g/mol and/or preferably with at most one phenolic group per molecule. You can.

Suitable examples of conformationally hindered phenols (C1) include 2,4-di-tert-butylphenol, 2,6-di-tert-butylphenol, 2-tert-butyl-4-methylphenol, 2,6-di -tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, 2,4,6-trimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,6 -di-tert-butyl-4-ethylphenol, 4,4'-methylenebis(2,6-di-tert-butylphenol), 3,5-di-tert-butyl-4-hydroxybenzyl alcohol, 3 ,5-di-tert-butylcatechol, 2,2-methylenebis(4-methyl-6-tert-butylphenol), 6-tert-butyl-2,4-xylenol, (ethane-1,2 -diylbis(oxy))bis(ethane-2,1-diyl)bis(3-(3-(tert-butyl)-4-hydroxy-5-methylphenyl)propanoate) (Irganox 245), pentaerys Lithyl-tetrakis(3-(3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)propionate) (Irganox® 1010), octyl-3,5-di-tert-butyl- 4-Hydroxyhydrocinnamate (Irganox 1135), 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-N'-[3-(3,5-di-tert-butyl-4 -Hydroxyphenyl)propanoyl]propanohydrazide (Irganox MD 1024), 2-methyl-4,6-bis(octylsulfanylmethyl)phenol (Irganox 1250L), 2,4-bis(dodecylthiomethyl )-6-methylphenol (Irganox 1726).

Besides the conformationally hindered phenol (C1), the composition according to the invention may comprise further suitable stabilizers, which act for example as UV and/or heat stabilizers. They are no longer limited in terms of structure. For example, cinnamic acid esters, benzophenone, diphenylcyan acrylate, formamidine, benzylidene malonate, daryl butadiene, triazine, HALS derivatives (hindered amine light stabilizers) and benzotriazole are UV and /or can be used as a heat stabilizer.

Additional examples of commercially available stabilizers are published in “Plastics Additive Handbook, ^5th Edition, ed., H. Zweifel, Hanser Publishers, Munich, 2001 ([1]), p. 98-136.

In the composition according to the invention, the structurally hindered phenol (C1) is present in a proportion of 0.001 to 3 wt%, preferably 0.01 to 1 wt%, based on the total weight of components (A) to (E) of the composition. . Other stabilizers may also be present in the composition in a proportion of 0 to 5 wt% based on the weight of components (A) to (E).

Ingredient (D): Synergist

In addition to components (A) to (C), the composition according to the invention comprises at least one synergist (D) based on a carbon allotrope with unsaturated carbon-carbon bonds.

Surprisingly, it has been found that the presence of synergist (D) in the composition according to the invention makes it possible to achieve a treatment time at room temperature of at least 48 hours, preferably at least 120 hours and particularly preferably at least 168 hours.

In the composition according to the invention, component (D) is preferably present in dispersed form.

The synergist (D) may be selected from common allotropic carbon modifications, provided that the carbon allotrope has unsaturated carbon-carbon bonds.

In one embodiment of the invention, the synergist (D) is selected from the group consisting of soot, graphite, graphene, fullerene, carbon nanotube (CNT), carbon nanohorn (CNH), and mixtures thereof. It can be.

The use of soot, graphite and/or graphene is particularly preferred.

Examples of suitable commercially available carbon allotropes for use as synergist (D) include Lamb Black 101 Powder, Printex 60 Powder or Special Black 100 from Orion Engineered Carbons.

Allotropes of carbon with predominantly saturated carbon-carbon bonds, such as diamond, are not suitable for use as synergists in the compositions according to the invention. Unsaturated carbon compounds such as anthracene or perylene are also not suitable as synergists (D).

In the composition according to the invention, the synergist (D) is present in a proportion of 0.01 to 10 wt%, preferably 0.05 to 5 wt%, based on the total weight of components (A) to (E) of the composition.

Ingredient (E): Additives

Additionally, the described compositions may contain optional components as further additives (E). Additives (E) are preferably fillers, colorants, pigments, anti-aging agents, fluorescent agents, polymerization accelerators, sensitizers, adhesion promoters, desiccants, crosslinking agents, flow improvers, wetting agents, thixotropic agents, diluents, softeners, polymers. It is selected from the group consisting of thickeners, flame retardants, corrosion inhibitors, plasticizers and tackifiers, and combinations thereof.

In the composition according to the present invention, additive (E) may be contained in a ratio of 0 to 85 wt%, preferably 1 to 65 wt%, based on the total weight of the composition.

In the meaning of the present invention, synergists (D) are not considered additives, especially fillers, colorants or pigments.

Addition reactive resin composition

The thermosetting composition according to the present invention formed by the above-described components (A) to (E) can be used alone or in combination with an addition reactive resin composition. Addition reactive resin compositions are no longer limited in terms of their chemical structures and compositions. In particular, the addition reactive resin composition may include, as reactive components, an addition reactive resin (F), a curing agent (G), and/or an initiator (H) for polymerization or crosslinking of the addition reactive resin (F).

Thereafter, the addition-reactive resin composition present in the mixture with the thermosetting composition according to the invention comprising components (A) to (E) is made dimensionally stable by heating and activating the thermosetting composition according to the invention at a low temperature. The state is fixed and can proceed to further processing steps.

Below, the components of the addition reactive resin composition will be explained in detail.

Component (F): Addition reactive resin

For example, at least one cationically polymerizable or addition-crosslinkable compound selected from the group consisting of epoxy-containing compositions (F1), oxetane (F2) and vinyl ether (F3), and combinations thereof is used as component (F). can be used

Epoxy-containing compounds (F1):

In the addition reactive resin composition, at least one epoxy-containing compound (F1) can be used as the addition reactive resin, which may be mono- or di-functional or higher functional.

For example, the epoxy-containing compound (F1) may include alicyclic epoxides, aromatic and aliphatic glycidyl ethers, glycidyl esters or glycidyl amines and mixtures thereof.

Preferably, the addition reactive resin comprises one or several at least difunctional epoxy-containing compounds. Here, “at least bifunctional” means that the epoxy-containing compound contains at least two epoxy groups.

In addition to at least bifunctional epoxy-containing compounds, monofunctional epoxides can also be used as reactive diluents.

Combinations of several epoxy-containing compounds, at least one of which is di- or higher-functional, are also within the meaning of the present invention.

Bifunctional alicyclic epoxy resins are known to the state of the art and contain compounds having both an alicyclic group and at least two oxirane rings. Representative examples include 3-cyclohexenylmethyl-3-cyclohexylcarboxylate diepoxide, 3,4-epoxycyclohexylalkyl-3',4'-epoxycyclohexane carboxylate, 3,4-epoxy-6. -Methylcyclohexylmethyl-3',4'-epoxy-6-methylcyclohexane carboxylate, vinylcyclohexene dioxide, bis(3,4-epoxycyclohexylmethyl)adipate, dicyclopentadiene dioxide, and 1,2-epoxy-6-(2,3-epoxypropoxy)hexahydro-4,7-methane indane and mixtures thereof.

Aromatic epoxy resins can also be used in addition reactive resin compositions. Examples of aromatic epoxy resins include bisphenol-A epoxy resin, bisphenol-F epoxy resin, phenol-novolac epoxy resin, cresol-novolac epoxy resin, biphenyl epoxy resin, 4,4'-biphenyl epoxy resin, divinylbenzene. Dioxide, 2-glycidylphenyl glycidyl ether, naphthalenediol diglycidyl ether, glycidyl ether of tris(hydroxyphenyl)methane and glycidyl ether of tris(hydroxyphenyl)ethane and these It is a mixture. Additionally, all fully or partially hydrogenated analogues of aromatic epoxy resins can also be used.

Isocyanurates substituted with epoxy-containing groups and other alicyclic compounds can also be used in addition reactive resin compositions. Examples include triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate.

Additionally, multifunctional epoxy resins of all resin groups, viscoplastic epoxy resins and mixtures of various epoxy resins can be used in the addition reactive resin composition.

Examples of commercially available epoxy-containing compounds include CELLOXIDE ^TM 2021P, CELLOXIDE ^TM 8000 from Daicel Corporation, Japan, EPIKOTE ^TM RESIN 828 LVEL, EPIKOTE ^TM RESIN 166, EPIKOTE ^TM RESIN 169 from Momentive Specialty Chemicals BV, the Netherlands, and Leuna Harze, Germany. Epilox ^TM resins from product series A, T and AF, or EPICLON ^TM 840, 840-S, 850, 850-S, EXA850CRP, 850-LC from DIC KK of Japan, Omnilane 1005 and Omnilane 2005 from IGM Resins BV. , Syna Epoxy 21 and Syna Epoxy 06 from Synasia Inc., Jiangsu Tetra New Material Technology Co. Ltd. under the trade names TTA21, TTA26, TTA60 and TTA128.

Oxetane (F2)

Instead of or in addition to the epoxy-containing compound (F1), preferably the oxetane-containing compound (F2) can be used in the addition reactive resin composition as the cationic or addition-curable component (F). The process for producing oxetane is known in particular from US 2017/0198093 A1.

Examples of commercially available oxetanes include bis(1-ethyl-3-oxetanylmethyl) ether (DOX), 3-allyloxymethyl-3-ethyl oxetane (AQX), 3-ethyl-3-[( Phenoxy)methyl oxetane (POX), 3-ethyl-3-hydroxymethyl oxetane (OXA), 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene (XDO), It is 3-ethyl-3-[(2-ethylhexyloxy)methyl]oxetane (EHOX). The named oxetane is commercially available from TOAGOSEI CO., LTD. Oxetanes of higher functionality are also within the meaning of the present invention.

Vinyl ether (F3):

Instead of or in addition to components (F1) and (F2), vinyl ether (F3) can be used as a cationic or addition-curable compound in the addition reactive resin composition.

Preferably, the addition reactive resin comprises one or several at least difunctional vinyl ethers. Here, “at least bifunctional” means that the vinyl ether contains at least two vinyl groups.

Suitable vinyl ethers include trimethylolpropane trivinyl ether, ethylene glycol divinyl ether, triethylene glycol divinyl ether (DVE-3), 1,4-butanediol divinyl ether (BDDVE), 1,4-cyclohexanedimethanol divinyl ether Vinyl ether (CHDM-di), 1,2,3-tris(vinyloxy)propane, 1,3,5-tris[(2-vinyloxy)ethoxy]benzene, tris[4-(vinyloxy)butyl] -1,2,4-Benzene tricarboxylate, 1,3,5-tris(2-vinyloxyethyl)-1,3,5-triazine, 1,3,5-cyclohexane trimethanol trivinyl ether , 1,1,1-tris-4-[2-(vinyloxy)ethoxy]phenylethane, tetrakis(vinyloxymethyl)methane and cyclic vinyl ethers and mixtures thereof. Additionally, vinyl ethers of polyfunctional alcohols can be used.

Hybrid Compound (F4):

In one embodiment, the addition reactive resin may include at least one hybrid compound (F4). The hybrid compound is characterized by having at least one cationically polymerizable or addition-crosslinkable group of components (F1) to (F3) and at least one (meth)acrylate group. Therefore, a hybrid compound is a compound of mixed functionality.

Preference is given to hybrid compounds (F4) which, in addition to the vinyl or epoxy groups mentioned, have additional (meth)acrylate functionality; Epoxy acrylate hybrid monomers are particularly preferred.

Examples of commercially available epoxy (meth)acrylates are CYCLOMER M100 from Daicel, Epoxy Acrylat Solmer SE 1605 and UVACURE 1561 from UCB, Miramer PE210HA from Miwon Europe GmbH and Solmer PSE from Soltech Ltd. It is 1924. There are also oxetane (meth)acrylates such as Eternacoll OXMA from UBE Industries LTD.

In the addition reactive resin composition, the addition reactive resin (F1) to (F4) is 20 to 99.99 wt%, preferably 30 to 70 wt% or 92 to 99.99 wt%, based on the weight of components (F) to (H). It may be contained in a ratio of .

Hardener (G):

Additionally, the addition reactive resin composition may contain a curing agent (G) for crosslinking the component (F) by, for example, addition polymerization. Hardeners are no longer limited in terms of chemical properties.

For example, nitrogen-containing compounds (G1) can be used as curing agents (G) for curing the addition-crosslinkable component (F), especially the epoxy-containing component (F1). Other possible curing agents are thiols and/or anhydrides.

Examples of suitable nitrogen-containing compounds include amines, especially aliphatic polyamines, arylaliphatic polyamines, alicyclic polyamines, aromatic polyamines and heterocyclic polyamines, and imidazoles, cyanamides, polyureas, Mannich bases, polyether polyamines, Includes polyaminoamides, phenalcamines, sulfonamides, aminocarboxylic acids or combinations of the classes of substances named.

Epoxides and/or anhydrides and reaction products of the nitrogen-containing compounds described above can also be used as curing agents (G).

In the addition reactive resin composition, the curing agent (G) may be contained in a ratio of 20 to 80 wt%, preferably 30 to 70 wt%, based on the weight of components (F) to (H).

Preferably, the addition-crosslinking reactive resin composition does not contain a cationic polymerization initiator (H).

Additional initiator (H):

The addition reactive resin composition can be formulated as a cationically polymerizable composition. In this case, the addition reactive resin composition may contain, in addition to the component (F), an addition initiator (H) for cationic polymerization of the addition reactive resin (F). Preferably, the additional initiator is a photolatent acid (H1) that can be activated by exposure to actinic radiation and includes, for example, initiators based on metallocenium and/or onium compounds. .

An overview of various metallocenium salts is disclosed in EP 0 542 716 B1. HSO ₄ ^- , PF ₆ ^- , SbF ₆ ^- , AsF ₆ ^- , Cl ^- , Br ^- , I ^- , ClO ₄ ^- , PO ₄ ^- , SO ₃ CF ₃ ^- , OTs- (tosylate), aluminate and borate. Anions (such as BF ₄ - and B(C ₆ F ₅ ) ₄ -) can be named as examples of various anions of metallocenium salts.

Preferably, the photopotential acids based on metallocenium compounds are selected from the group of ferrocenium salts.

Preferred onium compounds are selected from the group of arylsulfonium salts and aryliodonium salts and combinations thereof and are described in the state of the art.

Triarylsulfonium-based photoinitiators that are commercially available as photopotential acids include Chivacure 1176, Chivacure 1190 from Chitech, Irgacure 290, Irgacure 270, Irgacure GSID 26-1 from BASF, Speedcure 976 and Speedcure from Lambson. 992, TTA UV-692, TTA UV-694 from Jiangsu Tetra New Material Technology Co., Ltd. or UVI-6976 and UVI-6974 from Dow Chemical Co., Ltd.

Diaryliodonium-based photoinitiators that are commercially available as photopotential acids are available, for example, under the trade names UV1242 or UV2257 from Deuteron and Bluesil 2074 from Bluestar.

The photopotential acid (H1) used in the addition reactive resin composition is preferably activatable by actinic radiation with a wavelength of 200 to 480 nm.

Instead of or in addition to the light latent acid (H1), the addition reactive resin composition may also contain a thermally latent acid (H2) as an addition initiator for cationic polymerization. For example, the quaternary N-benzylpyridinium salts and N-benzylammonium salts disclosed in EP 0 343 690 or WO 2005/097883 are suitable as heat latent acids. Furthermore, thermally latent sulfonium salts as described in WO 2019/043778 A1 can be used as acid generators.

Commercially available products include K-PURE CXC-1614 or K-PURE CXC-1733 from King Industries Inc.; It is available from SAN-SHIN Chemical Industry Co., Ltd. under the trade names SAN-AID SI-80L and SAN-AID SI-100L.

Additionally, various metal chelate complexes based on titanium or aluminum can be used as thermally potent acids.

In the addition reactive resin composition, the addition initiator (H) is present in a proportion of 0.01 to 10 wt%, preferably 0.01 to 5 wt% and particularly preferably 0.1 to 3 wt%, based on the weight of components (F) to (H). It may be contained. Preferably, the cationic polymerization reactive resin composition does not contain a curing agent (G).

Preparation of composition according to the invention

The formulation of the thermosetting composition according to the invention comprises at least components (A) to (D). Additionally, additives (E) may be optionally contained.

In one embodiment, the composition according to the invention consists of components (A) to (D) and optionally component (E).

In another embodiment, the composition according to the present invention may be present in a mixture with an addition reactive resin composition consisting of components (F) to (H).

In a first preferred embodiment, the thermosetting composition according to the invention comprises the following components, each based on the total weight of components (A) to (E):

(A) 10 to 90 wt% of (meth)acrylates, especially 5 to 60 wt% of monofunctional (meth)acrylates, and/or 1 to 50 wt%, preferably 1 to 40 wt% of at least difunctional ( meth)acrylates or higher functional (meth)acrylates;

(B) 0.2 to 5 wt% of peroxodicarbonate;

(C) 0.01 to 1 wt% of at least one stabilizer selected from the group of conformationally hindered phenols;

(D) 0.01 to 5 wt% of a synergist based on a carbon allotrope with unsaturated carbon-carbon bonds, wherein the carbon allotrope preferably comprises a soot;

(E) 0 to 85 wt%, preferably 5 to 65 wt% of additional additives

It contains or consists of these ingredients.

In a second preferred embodiment, the composition according to the invention is preferably a mixture with an addition reactive resin composition. In particular, the composition according to the invention may have the composition described above for the first embodiment.

In particular, the addition reactive resin composition of the second embodiment is a cationic polymerization reactive resin composition and contains the following components:

(F) 92 to 99.99 wt% of an additional resin component (F) comprising at least one bifunctional epoxy-containing compound (F1) selected from the group of alicyclic epoxides, aliphatic and/or aromatic glycidyl ethers;

(H) 0.01 to 8 wt% of a cationic polymerization initiator selected from the group of light latent or heat latent acidifying agents.

Contains or consists of these ingredients,

The ratios of (F) and (H) in the addition reactive resin composition add up to 100%.

A preferred formulation of the second embodiment contains the following ingredients:

(A) 10 to 90 wt % of (meth)acrylates, especially 5 to 60 wt % of monofunctional (meth)acrylates, and/or 1 to 30 wt % of at least difunctional (meth)acrylates or higher functionality as crosslinker. soluble (meth)acrylate;

(B) 0.2 to 5 wt% of peroxodicarbonate;

(C) 0.01 to 1 wt% of at least one stabilizer selected from the group of conformationally hindered phenols;

(D) 0.01 to 5 wt% of a synergist based on a carbon allotrope with unsaturated carbon-carbon bonds, wherein the carbon allotrope preferably comprises a soot;

(E) 5 to 85 wt% of additional additives

A thermosetting composition consisting of,

The thermosetting composition, wherein the sum of the proportions of components (A) to (E) of the thermosetting composition adds up to 100%; and

Ingredients:

(F) 92 to 99.9 wt% of an addition reactive resin (F) comprising at least one bifunctional epoxy-containing compound (F1) selected from the group of alicyclic epoxides, aliphatic and/or aromatic glycidyl ethers; and

(H) 0.01 to 5 wt% of a cationic polymerization initiator selected from the group of light latent or heat latent acidifying agents.

A cationic polymerization reactive resin composition comprising,

It includes the cationic polymerization reactive resin composition, wherein the ratio of components (F) and (H) in the cationic polymerization reactive resin composition adds up to 100%,

The proportion of the thermosetting resin containing components (A) to (E) in the formulation is 10 to 90 wt%, and the proportion of the cationic polymerization reactive resin composition consisting of components (F) and (H) is 10 to 90 wt%.

Compositions according to the invention may be provided in both single-component and multi-component forms.

In a third embodiment, the thermosetting composition according to the invention is provided as a multi-component composition and comprises the following components, which are distributed in two packaging units (PU1 and PU2), each packaging unit (PU1) and PU2), the weight is indicated based on the total weight.

Packaging unit (PU1) :

(A) 10 to 80 wt % of a monofunctional (meth)acrylate and/or 10 to 50 wt % of at least a difunctional (meth)acrylate or a higher functionality (meth)acrylate as a crosslinker;

(C) 0.01 to 0.1 wt% of at least one stabilizer selected from the group of conformationally hindered phenols;

(D) 0.01 to 1 wt% of a synergist based on carbon allotropes with unsaturated carbon-carbon bonds, preferably soots;

(E) 0 to 40 wt% of additives.

Packaging unit (PU2) :

(B) 1 to 50 wt% of peroxodicarbonate; and

(E) 50 to 99 wt% of additives.

Typically, the packaging units (PU1 and PU2) are 10:1 to 1:1 (PU1:PU2) such that the ratio of peroxodicarbonate ranges from about 0.2 to 5 wt% based on the total weight of the easily mixed composition. ) are mixed in a ratio of

Characteristics of the composition according to the invention:

The thermosetting compositions according to the invention are characterized by high reactivity and at the same time long processing times at room temperature.

The composition can be cured in a short time at temperatures below 100°C, preferably below 90°C and more preferably below 80°C. Typically, the composition is fully cured within 5 minutes at a temperature of 100°C, within 15 minutes at 90°C and within 30 minutes at 80°C. Curing at 60℃ is also possible.

At the same time, the composition has a processing time at room temperature of at least 72 h, preferably at least 120 h and particularly preferably at least 168 h.

At a temperature of -18°C, the composition can be stored for at least 3 months without any reduction in processing time at room temperature.

In addition to its reactivity and long processing times, the cured composition is characterized by high adhesion to difficult-to-bond plastics. This is especially true for polyethylene (PE), polypropylene (PP), polycarbonate (PC), acrylonitrile-butadiene-styrene copolymer (ABS), polystyrene (PS), liquid crystal polymer (LCP) and cyclic olefin polymer (COP) and Includes plastic mixtures of polycarbonate/acrylonitrile-butadiene-styrene (PC/ABS). In particular, when bonding substrates based on polycarbonate, strengths of more than 8 MPa, preferably more than 10 MPa and particularly preferably more than 15 MPa are achieved.

The strength, especially the compressive shear strength, and the adhesive properties of the cured composition can be set over a wide range, in particular by varying component (A).

Use of thermosetting compositions according to the invention

Due to the low curing temperature, the compositions according to the invention are particularly suitable for temperature-sensitive bonding or encapsulation processes. Accordingly, especially optical or electronic substrates that withstand only limited heat input can be reliably joined, coated, encapsulated or bonded by using the compositions according to the invention. Despite the low curing temperature, high strength can be achieved even on low surface energy substrates, enabling the production of parts with high lifetime reliability.

Due to the long processing time at room temperature, the composition can also be easily used in complex industrial processes even after long downtimes and does not need to be removed from the plant and transferred to cold storage cells during extended dosing outages.

In particular, the composition according to the invention is suitable for use in optoelectronics. A possible use is the bonding of optical devices such as lenses.

Methods of using compositions according to the invention

According to the invention, a thermosetting composition is used to bond, encapsulate or coat a substrate, the method comprising the following steps:

a) providing a composition according to the invention;

b) dosing the composition onto a first substrate;

c) optionally supplying a second substrate to the composition;

d) optionally fixing the composition by exposure to actinic radiation; and

e) curing the composition while heating the composition and the substrate and/or substrate composite at a temperature of 60 to 100° C. for 5 to 60 minutes.

Measurement methods and regulations used

inspection

For the purposes of investigation, compositions according to the invention were prepared by DELO Industrie Klebstoffe GmbH & Co. It was irradiated with an intensity of 200 ± 20 mW/cm ² at a wavelength of 400 nm by an LED lamp of the DELOLUX series from KGaA.

room temperature

Room temperature is specified as 23±2℃.

Determination of Viscosity

Viscosity was measured using a Physica MCR302 rheometer from Anton Paar with a standardized PP20 measuring cone with 200 μm slots at a shear rate of 10 per second at 23°C.

processing time

To determine the processing time, all components of each composition were mixed at room temperature at 6 h intervals and the viscosity was checked within the first 24 h after preparation. The viscosity was then checked every 24 h. If the viscosity increased by more than 30% compared to the viscosity initially measured immediately after curing or manufacture of the composition in the container, the time previously established as suitable was determined as the maximum processing time.

compressive shear strength

Two specimens made of polycarbonate (dimensions 20 mm * 20 mm * 5 mm) were bonded using each composition with an overlap of 5 mm. For this purpose, a bead of the composition was applied to the first specimen and spread in a thin layer. Then, the second specimen was joined. The thickness and overlap of the adhesive layer of 0.1 mm were set by the bonding device. The bonded specimen was cured at 80°C for 30 minutes. Before curing, the minimum adhesive throat seam of the specimen can be fixed by light curing, which is carried out under conditions that ensure that the adhesive in the actual bonding area remains completely uncured. The strength below 6 MPa is insufficient, the strength between 6 and 8 MPa is bad, the strength between 8 and 10 MPa is sufficient, the strength between 10 MPa and 20 MPa is good, and the strength above 20 MPa is very good.

DSC measurements

DSC measurements of reactivity were performed using a differential scanning calorimeter (DSC) of type DSC 822e or DSC 823e from Mettler Toledo.

For this purpose, a liquid sample of 6 to 10 mg is weighed into an aluminum crucible (40 μL) using a pin, sealed with a perforated lid and measured over a temperature range of 40 to 130° C. at a heating rate of 1 K/min. The process gas is nitrogen (volume flow rate 50 mL/min).

Evaluate peak temperature.

Preparation of Curable Compositions

First, the liquid components are mixed, then fillers and optionally additional solids are incorporated using a laboratory stirrer, laboratory dissolver or speed mixer (Fa. Hauschild) until a homogeneous composition is formed. Accordingly, compositions that contain photoinitiators and are sensitive to visible light must be prepared using light of an excitation wavelength in addition to that used for the photoinitiator or sensitizer. The peroxo compound (B) is added at the end of preparation and the composition is mixed at controlled temperature. Preferably the temperature does not exceed 30°C.

The composition thus prepared was filled into a single-chamber cartridge or a multi-chamber cartridge and sealed.

Illustrative Embodiments and Comparative Examples

In the following, compositions according to the invention were prepared and their properties were compared with selected comparative examples and compositions from the state of the art. The results are shown in Tables 1 to 3. In the table, amounts are given in wt%.

In the list below, all compounds used to prepare the compositions and their abbreviations are identified.

Ingredient (A): Radical curable compound

(A1) Isobornyl acrylate (IBOA) (available from Sigma Aldrich)

(A2) Isobornyl methacrylate (IBOMA) (available from Sigma Aldrich)

(A3) Acrylic acid (available from Sigma Aldrich)

(A4) N,N-dimethyl acrylamide (available from Sigma Aldrich)

(A5) UV 3200B (urethane acrylate, available from Mitsubishi Chemical Corporation)

(A6) Miramer M1530 (propoxylated THF acrylate, available from Miwon)

(A7) PEAM-645 (polyester acrylate, available from Designer Molecules)

(A8) SR833S (bifunctional alicyclic acrylate, available from Sartomer)

Component (B): Radical polymerization initiator

(B1-1) tert-butylperoxy neodecanoate (available from Pergan (trade name: Peroxan PND))

(B1-2) di(2-ethylhexyl) peroxodicarbonate (available from United Initiators (trade name: EHPC-75-AL))

(B1-3) di(4-tert-butylcyclohexyl) peroxodicarbonate (available from United Initiators (trade name: BHPC))

(B2-1) 2,4,6-trimethylbenzoyldiphenylphosphine oxide (available from BASF (trade name: TPO-L))

(B2-2) diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide (available from BASF (trade name: TPO))

(B2-3) 2-Hydroxy-2-methyl propiophenone (available from IGM Resins (trade name: Omnirad 73))

Ingredient (C): Stabilizer

(C1) 2,6-di-tert-butyl-4-methylphenol (BHT) (available from Sigma Aldrich)

(C2) 4-methoxyphenol (HQMME) (available from Sigma Aldrich)

(C3) Phenothiazine (available from Sigma Aldrich)

(C4) 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO) (available from Sigma Aldrich)

Ingredient (D): Synergist

(D1) Special Black 100 (available from Continental Carbon Company)

Ingredient (E): Additives

(E1) HDK H2000 (fumed silica, available from Wacker)

(E2) Aerosil R 208 (fumed silica coated with polydimethyl siloxane, available from Evonik)

(E3) (3-glycidyloxypropyl)trimethoxysilane (available from Evonik (trade name Dynasilan Glymo))

(E4) SFP-30M (fumed silica, available from Denka)

(E5) San-Aid SI-S stabilizer (available from Sanshin Chemical Industry Co. Ltd.)

Component (F): Addition reactive resin: Epoxy-containing compound (F1) and oxetane (F2):

(F1-1) Epikote Resin 169 (bisphenol-A/F glycidyl ether, available from Hexion)

(F1-2) Celloxide 2021P (alicyclic epoxide, available from Daicel)

(F1-3) jER YL 980 (bisphenol-A glycidyl ether, available from Mitsubishi Chemicals)

(F2-1) Bis[1-ethyl(3-oxetanyl)]methyl ether (available from Toagosei (trade name: OXT 221))

Hardener (G):

(G1-1) Adeka EH-5057PK (polyamine, available from Adeka)

Cationic polymerization initiator (H):

(H2-1) K-Pure CXC-1821 (thermal acid generator, available from King Industries)

Table 1 shows Examples E1 to E7 and Comparative Examples R1 to R9 side by side according to the present invention. Examples E1 and E7 according to the invention, due to the advantageous combination of components (A) to (D) in the curable composition based on acrylates, achieve a DSC peak temperature of 72° C., simultaneously with a long treatment time of at least 168 hours at room temperature. It shows that a low curing temperature characterized by can be achieved (Figure 1). In addition, compositions E1 and E7 according to the invention provide high strengths of 37 MPa and 40 MPa, respectively, to polycarbonate in the cured state. Example E2 similarly shows that similar behavior can be achieved with methacrylate-containing systems.

The DSC peak temperature can be further lowered by reducing stabilization by adding 0.05 wt% of stabilizer (C1) (Example E3) without the processing time at room temperature falling below 3 days. At the same time, remarkable strengths continue to be achieved when bonding polycarbonate.

Higher proportions of stabilizer (C1) (0.2 wt%) increase the processing time up to 2 weeks, as shown in Example E4. Nonetheless, high reactivity (DSC peak temperature 77°C) is maintained. The composition according to the invention can be processed even after two weeks of storage at room temperature and can be cured indefinitely below 80°C.

However, as soon as the addition of stabilizers is omitted (comparative example R4) or only stabilizers not selected from the group of conformationally hindered phenols are used (see R5, R6 and R7), the treatment time at room temperature is 24 h. falls below For example, Comparative Example R6 only shows an unacceptable processing time of less than 1 hour when no conformationally hindered phenol is used as stabilizer (C).

Surprisingly, even when no synergist (D1) is used, the treatment time is shortened to up to 24 h, as shown in Comparative Example R2. Without component (D1), each formulation is unstable at room temperature (DSC peak temperature 49°C). Comparative example R3 shows that the reduced stability at room temperature cannot be compensated for by higher amounts of stabilizer. At the same time, if component (D1) is omitted, in both examples R2 and R3 only moderate strengths are achieved when bonding plastics.

However, when components (A) to (D) are combined in the sense of the present invention, only 0.01 wt% of synergist (D) is sufficient to achieve the three advantageous properties of stability, reactivity and adhesion (Example E5) .

If the stabilizer (C1) is omitted in addition to the synergist (D1) (Comparative Example R1), the processing time is too short to properly handle the formulation at room temperature.

Figure 1 shows DSC curves of Examples and Comparative Examples R1, R2 and R4 according to the present invention. The compositions of Comparative Examples R1, R2 and R4 formulated without synergists and/or stabilizers have DSC peak temperatures close to room temperature. Accordingly, these compositions exhibit insufficient processing time at room temperature and therefore cannot be formulated stably. In contrast, composition E1 according to the invention shows a balanced profile of reactivity and stability properties. Composition E1 can be cured at lower temperatures while remaining processable at room temperature.

As a component enabling curing at low temperatures, the composition includes at least one peroxodicarbonate as a radical polymerization initiator. Omitting the peroxodicarbonate and using only alternative peroxides as initiators (Comparative Examples R8 and R9) results in low stability formulations that exhibit unacceptably poor adhesion values in the cured state, especially to polycarbonates. obtained. Addition of synergist (D1) in combination with other peroxides did not improve stability and/or adhesion (Comparative Example R9).

Table 2 includes formulation E3 from WO 2018/089494 A1 as a comparative example. In Comparative Example R11, 0.15 wt% of synergist (D1) is used, but no structurally hindered phenol is used as stabilizer (C1). The cured composition from WO 2018/089494 A1 achieves high strengths against polycarbonate, but it has the disadvantage of a short processing time at room temperature of less than 24 h. In contrast, example E8 according to the invention additionally contains a stabilizer (C1) and thus achieves a treatment time of 7 days at a DSC peak temperature of 70°C. By adding a radical photoinitiator, the composition from example E8 can be further fixed by exposure to light.

According to Comparative Example R10, which corresponds to Example E6 from WO 2018/089494 A1, when using only the proposed stabilizer (C2) without adding stereotactically hindered phenols, the treatment time at room temperature is substantially improved. 24h, which is much lower than the advantageous 72h for compositions according to the present invention.

Table 3 shows a second embodiment of the present invention. Example E9 is a formulation having a cationic polymerization reactive resin composition further containing, in addition to epoxides (F1-2) and (F1-3), a thermal latent initiator for cationic polymerization (H2-1), component (A) ) to (E) can also be advantageously used.

Claims (12)

A thermosetting composition comprising:
Ingredients:
(A) at least one radically curable compound, wherein the radically curable compound comprises at least one (meth)acrylate,
(B) at least one radical initiator based on a peroxo compound, wherein the peroxo compound comprises at least one peroxodicarbonate,
(C) at least one stabilizer comprising at least one sterically hindered phenol, and
(D) at least one synergist based on a carbon allotrope with unsaturated carbon-carbon bonds
A composition containing. In claim 1,
The at least one (meth)acrylate is selected from the group consisting of aliphatic, optionally linear or branched, alicyclic, aromatic and heterocyclic (meth)acrylates, and the (meth)acrylate is preferably used as a crosslinking agent. A composition comprising at least a monofunctional (meth)acrylate together with a difunctional (meth)acrylate. In claim 1 or claim 2,
The composition according to claim 1, wherein the structurally hindered phenol has a molar mass of less than 500 g/mol and/or a single phenol group per molecule. The method according to any one of claims 1 to 3,
The composition (D) is characterized in that it is selected from the group consisting of soot, activated carbon, graphene, graphite, fullerene, carbon nanotube, carbon nanohorn, and combinations thereof. The method according to any one of claims 1 to 4,
The thermosetting composition may contain at least one additional additive, preferably toughness modifiers, colorants, pigments, fluorescent agents, thixotropic agents, thickeners, stabilizers, antioxidants, plasticizers, tackifiers, catalysts, fillers, Composition, characterized in that it comprises at least one further additive from the group of flame retardants, desiccants, corrosion inhibitors, inert and reactive diluents, leveling agents and wetting agents or adhesion promoters. The method according to any one of claims 1 to 5,
The thermosetting composition contains the following components:
(A) 5-98 wt%, preferably 10 to 90 wt% or 0-85 wt% of a radically curable compound, wherein the radically curable compound comprises at least one (meth)acrylate;
(B) 0.01-10 wt%, preferably 0.1-5 wt% of a radical initiator, wherein the radical initiator comprises at least one peroxodicarbonate and optionally a radical photoinitiator in a proportion of 0.01 to 7 wt%;
(C) 0.001-3 wt%, preferably 0.01-0.1 wt% of structurally hindered phenol, and 0 to 5 wt% of other stabilizers;
(D) 0.01-10 wt%, preferably 0.05-5 wt%, of a synergist based on a carbon allotrope with unsaturated carbon-carbon bonds;
(E) 0-85 wt%, preferably 1 to 65 wt% of at least one further additive, preferably toughness modifiers, colorants, pigments, fluorescent agents, thixotropic agents, thickeners, stabilizers, antioxidants, plasticizers, tackifiers. At least one additional additive from the group of imparting agents, catalysts, fillers, flame retardants, desiccants, corrosion inhibitors, inert and reactive diluents, leveling agents and wetting agents or adhesion promoters.
Including,
A composition characterized in that the sum of the ratios of the components (A) to (E) adds up to 100%. The method according to any one of claims 1 to 6,
The thermosetting composition is present with an addition reactive resin composition, the addition reactive resin composition preferably comprising an addition resin selected from the group of epoxy-containing compounds, oxetane, vinyl ether and their hybrid compounds having (meth)acrylate groups. A composition comprising a reactive resin, and at least one curing agent and/or at least one cationic polymerization initiator. In claim 7,
Based on the total weight of the mixture of the thermosetting composition and the addition reactive resin composition, the proportion of the thermosetting composition containing components (A) to (E) is 10 to 90wt%, and the addition reactive resin composition is 10% by weight. A composition characterized in that it is present in a proportion of from 90 wt%. In claim 7 or claim 8,
The addition reactive resin composition contains the following components:
(F) up to 99.99 wt%, preferably 92-99.9 wt%, of addition reactive resin; and
(H) at least one photolatent or thermally active polymer of 0.001-8 wt%, preferably 0.01-5 wt% and particularly preferably 0.1-3 wt%, for cationic polymerization of the addition reactive resin. latent) acid generator
A composition comprising: The method according to any one of claims 1 to 9,
The composition has the following properties:
Full cure at temperatures up to 100°C in less than 5 minutes, up to 90°C in less than 15 minutes, up to 80°C in less than 30 minutes,
a treatment time at room temperature of at least 72 h, preferably at least 120 h, particularly preferably at least 168 h, and
Compressive shear strength after curing at 80°C for 30 minutes of greater than 8 MPa, preferably greater than 10 MPa, particularly preferably greater than 15 MPa.
A composition comprising at least one of the following: Use of the composition according to any one of claims 1 to 10 as a sealing, adhesive and/or encapsulant composition. A method of using the composition of claim 9 to bond, encapsulate or coat a substrate, comprising:
a) providing a composition according to any one of claims 1 to 11;
b) dosing the composition onto a first substrate;
c) optionally supplying a second substrate to the composition;
d) optionally fixing the composition by actinic irradiation; and
e) curing the composition while heating the composition and the substrate and/or substrate composite at a temperature of 60 to 100° C. for 5 to 60 minutes.
A method comprising: